(
)
L.-J. Baker et al.rJournal of Organometallic Chemistry 551 1998 247–259
255
n
.
Ž
.
Ž
bromonaphthalene were added to diethyl ether 20 ml
in a Schlenk tube. In a second Schlenk tube
.Ž
flask. A solution of BuLi in hexanes 1.25 M, 2.37 ml,
.
1.00 mole equivalent was added at room temperature.
Ž
.
Ž
.
Ž
.
1.00 g, 1.11 mmol was
n
Os 5CCl2 Cl2 CO PPh3
dissolved in thf 30 ml . A solution of BuLi in hexanes
Within seconds the pale yellow solution turned dark
yellow, and then a white solid crystallized. At this point
the round bottom flask was immediately cooled to
y788C. Ru 5CCl2 Cl2 CO PPh3
2
Ž
.
Ž
1.25 M, 4.79 ml, 1 mole equivalent relative to 2-
.
Ž
.
Ž
.Ž
.
Ž
bromonaphthalene was added at room temperature with
rapid stirring to the Schlenk tube containing the 2-
bromonaphthalene. After 15 s this mixture was cooled
to y788C. The 2-naphthyllithium thus formed was
titrated rapidly against diphenyl ketone tosylhydrazide
1.00 g, 1.24
2
.
Ž
.
mmol was dissolved in thf 30 ml in a Schlenk tube at
room temperature. The orange solution was rapidly
transferred by syringe in a single portion to the round
bottom flask. The orange solution immediately turned
greenish-brown. It was left at y788C for 5 min and
then removed from the cold bath. The solution was
allowed to warm to ca. 08C over a period of 10 min.
The volume of thf was then reduced to 10 ml under
Ž
Ž
..
w x
100 mg in thf 3 ml 14 . The Schlenk tube was
Ž
cooled to y408C and 2-naphthyllithium 1.10 mole
Ž
.
Ž
.Ž
. .
equivalents relative to Os 5CCl2 Cl2 CO PPh3 , was
2
added. The initial orange solution turned greenish-
brown. After 2 min at y408C the cooling bath was
removed and the solution was allowed to warm up to
08C over a period of 10 min. The volume of thf was
reduced to 10 ml under vacuum, and diethyl ether 50
ml was added to afford crystallisation of a bright green
microcrystalline solid. This was collected by filtration
and washed with water 20 ml , a 1:1 mixture of
water–ethanol 20 ml , and hexanes 20 ml . The prod-
uct was dried in vacuo to give pure 2 as a bright green
Ž
.
reduced pressure and diethyl ether 50 ml was added.
A light brown solid was collected by rapid filtration and
Ž
.
washed with water 20 ml , a 1:1 mixture of water–
Ž
Ž
.
Ž
.
Ž
ethanol 20 ml , ethanol 20 ml and finally hexane 20
ml . The product was dried in vacuo to give pure 4 as a
.
.
Ž
bright maize coloured microcrystalline solid, 145 mg,
14% . m.p. 1348C. Ms828.29 g moly1. This com-
Ž
.
.
Ž
.
Ž
.
pound could not be purified sufficiently to obtain satis-
factory elemental analysis but all derivatives obtained
and described below gave satisfactory elemental analy-
ses.
Ž
.
microcrystalline solid 920 mg, 91% . m.p. 1508C. Ms
917.42 g moly1. This compound could not be purified
sufficiently to obtain satisfactory elemental analysis but
all derivatives obtained and described below gave satis-
factory elemental analyses. 1H NMR: 7.0–8.5, unre-
[
(
)( ) (
) ]
( )
5
3.5. Os C-1-naphthyl CO 2 PPh3 ClO4
2
solved multiplet signals, PPh3 and 1-naphthyl. 13C
Ž
.
A solution of AgClO4 45.2 mg, 0.220 mmol in
dichloromethane 20 ml and ethanol 20 ml was pres-
surised with CO 4 atm for 1 min in a carbonylation
tube CAUTION: extreme care should be exercised in
the handling of solutions of perchlorates in the presence
of oxidisable materials as explosive mixtures could
result. Perchlorate salts of oxidisable cations such as
5–8 are also potentially explosive . The pressure was
released and Os [C-1-naphthyl Cl CO PPh3
2
Ž
.
Ž
.
Ž
Ž
.
.
Ž
.
NMR: 325.6, t, J CP s14.1, C carbyne 198.9, t,
2
Ž
.
J CP s10.1, CO.
Ž
(
)
(
)( ) ( )
3.3. Ru [CPh Cl CO PPh3 3
2
In a Schlenk tube and at room temperature,
Ru 5CCl2 Cl2 CO PPh3
dissolved in thf 30 ml . A solution of PhLi 2.00 ml,
1.25 M was added via a syringe to the orange solution.
Ž
.
Ž
.Ž
.
Ž
.
1.00 g, 1.24 mmol was
2
Ž
.
Ž
.
.
Ž
.
.
Ž
.Ž
.
Ž
200
2
The orange solution immediately turned greenish-brown.
The Schlenk tube was left at y788C for 5 min and then
removed from the cold bath. The solution was allowed
to warm to ca. 08C over a period of 10 min. The volume
of thf was then reduced to 10 ml under reduced pressure
mg, 0.220 mmol was added rapidly and the vessel
Ž
.
re-pressurised with CO 4 atm . The greenish solid
dissolved to give a red solution. CO pressure was
maintained for 15 min. After filtration through a Celite
pad to remove the precipitated AgCl, the solvent vol-
ume was cautiously reduced to ca. 20 ml on a rotary
evaporator without applying heat, in order to induce
crystallisation. After recrystallisation from
dichloromethane-ethanol the red crystals were collected
Ž
.
and diethyl ether 50 ml was added. A light brown
solid was collected by rapid filtration and washed with
Ž
.
Ž
.
water 20 ml , a 1:1 mixture of water–ethanol 20 ml ,
ethanol 20 ml and finally hexane 20 ml . The product
Ž
.
Ž
.
was dried in vacuo to give 3 as a dark green coloured
by filtration and washed with hexane to give pure 5,
y1
Ž
.
Ž
.
microcrystalline solid, 830 mg, 86% . m.p. 1348C.
Ms778.23 g moly1. This compound could not be
purified sufficiently to obtain satisfactory elemental
analysis but all derivatives obtained and described be-
low gave satisfactory elemental analyses.
150 mg, 68% . m.p. 1908C. Ms1009.43 g mol
Anal. Found: C, 55.82; H, 3.32% C49 H37ClO6OsP2 P
2r3CH2Cl2 CH2Cl2 evident in the 1H NMR spec-
Ž
1
.
trum requires C, 55.96; H, 3.62%. H NMR: 7.0–8.5,
unresolved multiplet signals, PPh3 and 1-naphthyl. 13C
2
Ž
.
Ž
.
NMR: 327.8, t, J CP s11.2, C carbyne 198.9, t,
(
)
(
)(
) ( )
3.4. Ru [C-1-naphthyl Cl CO PPh3 4
2
2
Ž
.
Ž
J CP s9.5, CO. A single crystal suitable for X-ray
Ž
.
.
1-Bromonaphthalene 0.414 ml, 2.96 mmol was
study see Section 3.21 was grown from CHCl3 and
Ž
.
stirred in diethyl ether 3 ml in a 100 ml round bottom
had the formula C49 H37ClO6OsP2 P2CHCl3.
Baker, Lisa-Jane
